Preparation and functionalization of cellulose nanofibers using a naturally occurring acid and their application in stabilizing linseed oil/water Pickering emulsions.

Finding efficient and environmental-friendly methods to produce and chemically modify cellulose nanofibers (CNFs) remains a challenge. In this study, lactic acid (LA) treatment followed by microfluidization was employed for the isolation and functionalization of CNFs. Small amounts of HCl (0.01, 0.1, and 0.2 M) were used alongside LA to intensify cellulose hydrolysis. FTIR spectroscopy and solid-state 13C NMR confirmed the successful functionalization of CNFs with lactyl groups during isolation, while SEM, AFM, and rheological tests revealed that the addition of HCl governed the fibers' sizes and morphology. Notably, the treatment with LA and 0.2 M HCl resulted in a more efficient defibrillation, yielding smaller nanofibers sizes (62 nm) as compared to the treatment with LA or HCl alone (90 and 108 nm, respectively). The aqueous suspension of CNFs treated with LA and 0.2 M HCl showed the highest viscosity and storage modulus. LA-modified CNFs were tested as stabilizers for linseed oil/water (50/50 v/v) emulsions. Owing to the lactyl groups grafted on their surface and higher aspect ratio, CNFs produced with 0.1 and 0.2 M HCl led to emulsions with increased stability (a creaming index increase of only 3 % and 1 %, respectively, in 30 days) and smaller droplets sizes of 23.4 ± 1.2 and 35.5 ± 0.5 µm, respectively. The results showed that LA-modified CNFs are promising stabilizers for Pickering emulsions.

Plant-Derived Nanocellulose with Antibacterial Activity for Wound Healing Dressing.

The medical sector is one of the biggest consumers of single-use materials, and while the insurance of sterile media is non-negotiable, the environmental aspect is a chronic problem. Nanocellulose (NC) is one of the safest and most promising materials that can be used in medical applications due to its valuable properties like biocompatibility and biodegradability, along with its good mechanical properties and high water uptake capacity. However, NC has no bactericidal activity, which is a critical need for the effective prevention of infections in chronic diabetic wound dressing applications. Therefore, in this work, a natural product, propolis extract (PE), was used as an antibacterial agent, in different amounts, together with NC to obtain sponge-like structures (NC/PE). The scanning electron microscope (SEM) images showed well-impregnated cellulose fibers and a more compact structure with the addition of PE. According to the thermogravimetric analysis (TGA), the samples containing PE underwent thermal degradation before the unmodified NC due to the presence of volatile compounds in the extract. However, the peak degradation temperature in the first derivative thermogravimetric curves was higher for all the sponges containing PE when compared to the unmodified NC. The antibacterial efficacy of the samples was tested against Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli, as well as on two clinically resistant isolates. The samples completely inhibited the development of Staphylococcus aureus, and Pseudomonas aeruginosa was partially inhibited, while Escherichia coli was resistant to the PE action. Considering the physical and biological properties along with the environmental and economic benefits, the development of an NC/PE wound dressing seems promising.

Nanocellulose Sponges Containing Antibacterial Basil Extract.

Nanocellulose (NC) is a valuable material in tissue engineering, wound dressing, and drug delivery, but its lack of antimicrobial activity is a major drawback for these applications. In this work, basil ethanolic extract (BE) and basil seed mucilage (BSM) were used to endow nanocellulose with antibacterial activity. NC/BE and NC/BE/BSM sponges were obtained from nanocellulose suspensions and different amounts of BE and BSM after freeze-drying. Regardless of the BE or BSM content, the sponges started to decompose at a lower temperature due to the presence of highly volatile active compounds in BE. A SEM investigation revealed an opened-cell structure and nanofibrillar morphology for all the sponges, while highly impregnated nanofibers were observed by SEM in NC/BE sponges with higher amounts of BE. A quantitative evaluation of the porous morphology by microcomputer tomography showed that the open porosity of the sponges varied between 70% and 82%, being lower in the sponges with higher BE/BSM content due to the impregnation of cellulose nanofibers with BE/BSM, which led to smaller pores. The addition of BE increased the specific compression strength of the NC/BE sponges, with a higher amount of BE having a stronger effect. A slight inhibition of S. aureus growth was observed in the NC/BE sponges with a higher amount of BE, and no effect was observed in the unmodified NC. In addition, the NC/BE sponge with the highest amount of BE and the best antibacterial effect in the series showed no cytotoxic effect and did not interfere with the normal development of the L929 cell line, similar to the unmodified NC. This work uses a simple, straightforward method to obtain highly porous nanocellulose structures containing antibacterial basil extract for use in biomedical applications.

Contribution of the Surface Treatment of Nanofibrillated Cellulose on the Properties of Bio-Based Epoxy Nanocomposites Intended for Flexible Electronics.

The growing interest in materials derived from biomass has generated a multitude of solutions for the development of new sustainable materials with low environmental impact. We report here, for the first time, a strategy to obtain bio-based nanocomposites from epoxidized linseed oil (ELO), itaconic acid (IA), and surface-treated nanofibrillated cellulose (NC). The effect of nanofibrillated cellulose functionalized with silane (NC/S) and then grafted with methacrylic acid (NC/SM) on the properties of the resulted bio-based epoxy systems was thoroughly investigated. The differential scanning calorimetry (DSC) results showed that the addition of NCs did not influence the curing process and had a slight impact on the maximum peak temperature. Moreover, the NCs improved the onset degradation temperature of the epoxy-based nanocomposites by more than 30 °C, regardless of their treatment. The most important effect on the mechanical properties of bio-based epoxy nanocomposites, i.e., an increase in the storage modulus by more than 60% at room temperature was observed in the case of NC/SM addition. Therefore, NC's treatment with silane and methacrylic acid improved the epoxy-nanofiber interface and led to a very good dispersion of the NC/SM in the epoxy network, as observed by the SEM investigation. The dielectric results proved the suitability of the obtained bio-based epoxy/NCs materials as substitutes for petroleum-based thermosets in the fabrication of flexible electronic devices.

Complex Effects of Hemp Fibers and Impact Modifiers in Multiphase Polypropylene Systems.

Natural fibers-reinforced polymer composites have progressed rapidly due to their undeniable advantages. Most of the commercial polypropylene (PP)-based materials are characterized by either high impact toughness or high stiffness, while the manufacture of PP composites with both good toughness and stiffness is challenging at present. In this work, poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) and poly(styrene-b-butadiene-b-styrene) (SBS) copolymers were used in different amounts as modifiers in PP/hemp fibers (HF) composites, with the aim to use them for electrical vehicle parts. The interface in these multiphase systems was controlled by the addition of maleated polypropylene (MAPP). SEBS and SBS showed different effects on the elongation at break of the blends and the corresponding composites due to the HF that stiffened the multiphase systems. Similarly, a different action of MAPP was observed in the composites containing SEBS or SBS: higher Young's and storage moduli were obtained for the composite containing SBS, while greater elongation at break and impact strength values were recorded for the SEBS-containing system. In addition, a remarkable dispersion in the MAPP-containing composite and two times smaller average particle size were revealed by the SEM analysis for the SEBS particles compared to the SBS ones. The higher affinity of SEBS for PP compared to that for SBS and the different morphological characteristics of the systems containing SEBS and SBS may explain the different effects of these impact modifiers on the mechanical properties of the composites. The composites developed in this work were designed as substitutes for the fully synthetic polymeric materials or metal components used in the manufacturing of automotive parts.

Opposite Roles of Bacterial Cellulose Nanofibers and Foaming Agent in Polyhydroxyalkanoate-Based Materials.

In this work, an economically feasible procedure was employed to produce poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)-based foams. Thermally expandable microspheres (TESs) were used as a blowing agent, while bacterial cellulose (BC) nanofibers served both as a reinforcing agent and as a means of improving biocompatibility. PHBV was plasticized with acetyltributylcitrate to reduce the processing temperature and ensure the maximum efficiency of the TES agent. The morphological investigation results for plasticized PHBV foams showed well-organized porous structures characterized by a porosity of 65% and the presence of both large pores (>100 µm) and finer ones, with a higher proportion of pores larger than 100 µm being observed in the PHBV nanocomposite containing TESs and BC. The foamed structure allowed an increase in the water absorption capacity of up to 650% as compared to the unfoamed samples. TESs and BC had opposite effects on the thermal stability of the plasticized PHBV, with TESs decreasing the degradation temperature by about 17 °C and BC raising it by 3−4 °C. A similar effect was observed for the melting temperature. Regarding the mechanical properties, the TESs had a flexibilizing effect on plasticized PHBV, while BC nanofibers showed a stiffening effect. An in vitro cytotoxicity test showed that all PHBV compounds exhibited high cell viability. The addition of TESs and BC nanofibers to PHBV biocomposites enabled balanced properties, along with lower costs, making PHBV a more attractive biomaterial for engineering, packaging, or medical device applications.

Bio-Based Poly(lactic acid)/Poly(butylene sebacate) Blends with Improved Toughness.

A series of poly(butylene sebacate) (PBSe) aliphatic polyesters were successfully synthesized by the melt polycondensation of sebacic acid (Se) and 1,4-butanediol (BDO), two monomers manufactured on an industrial scale from biomass. The number average molecular weight (Mn) in the range from 6116 to 10,779 g/mol and the glass transition temperature (Tg) of the PBSe polyesters were tuned by adjusting the feed ratio between the two monomers. Polylactic acid (PLA)/PBSe blends with PBSe concentrations between 2.5 to 20 wt% were obtained by melt compounding. For the first time, PBSe's effect on the flexibility and toughness of PLA was studied. As shown by the torque and melt flow index (MFI) values, the addition of PBSe endowed PLA with both enhanced melt processability and flexibility. The tensile tests and thermogravimetric analysis showed that PLA/PBSe blends containing 20 wt% PBSe obtained using a BDO molar excess of 50% reached an increase in elongation at break from 2.9 to 108%, with a negligible decrease in Young's modulus from 2186 MPa to 1843 MPa, and a slight decrease in thermal performances. These results demonstrated the plasticizing efficiency of the synthesized bio-derived polyesters in overcoming PLA's brittleness. Moreover, the tunable properties of the resulting PBSe can be of great industrial interest in the context of circular bioeconomy.

Poly(3-hydroxybutyrate) Nanocomposites with Cellulose Nanocrystals.

Poly(3-hydroxybutyrate) (PHB) is one of the most promising substitutes for the petroleum-based polymers used in the packaging and biomedical fields due to its biodegradability, biocompatibility, good stiffness, and strength, along with its good gas-barrier properties. One route to overcome some of the PHB's weaknesses, such as its slow crystallization, brittleness, modest thermal stability, and low melt strength is the addition of cellulose nanocrystals (CNCs) and the production of PHB/CNCs nanocomposites. Choosing the adequate processing technology for the fabrication of the PHB/CNCs nanocomposites and a suitable surface treatment for the CNCs are key factors in obtaining a good interfacial adhesion, superior thermal stability, and mechanical performances for the resulting nanocomposites. The information provided in this review related to the preparation routes, thermal, mechanical, and barrier properties of the PHB/CNCs nanocomposites may represent a starting point in finding new strategies to reduce the manufacturing costs or to design better technological solutions for the production of these materials at industrial scale. It is outlined in this review that the use of low-value biomass resources in the obtaining of both PHB and CNCs might be a safe track for a circular and bio-based economy. Undoubtedly, the PHB/CNCs nanocomposites will be an important part of a greener future in terms of successful replacement of the conventional plastic materials in many engineering and biomedical applications.